This invention relates to the field of water-soluble polymers incorporating fluorescent moieties. The fluorescent monomers incorporated into the polymers are also disclosed. In addition, a method for determining the efficiency of polymers incorporating fluorescent moieties as water treatment agents is also disclosed.
In many fields that employ polymers it may be desirable to tag or mark such polymers to facilitate monitoring thereof. By the term xe2x80x9cmonitoringxe2x80x9d is meant herein any type of tracing or tracking to determine the location or route of the polymers, and any type of determination of the concentration or amount of the polymer at any given site, including singular or intermittent or continuous monitoring. For instance, it may be desirable to monitor water treatment polymers in water systems, or to monitor polymers that may be present in waste fluids before disposal, or to monitor the polymer used for down-hole oil well applications, or to monitor polymers that may be present in fluids used to wash a manufactured product.
As seen from the above list of possible applications of polymer monitoring, the purpose of such monitoring may be to trace or track or determine the level of the polymer itself, or to trace or track or determine the level of some substance in association with the polymer, or to determine some property of the polymer or substance in association with the polymer, for instance its leachability.
Conventional techniques for monitoring polymers are generally time-consuming and labor intensive, and often require the use of bulky and/or costly equipment. Most conventional polymer analysis techniques require the preparation of calibration curves for each type of polymer employed, which is time-consuming and laborious, particularly when a large variety of polymer chemistries are being employed, and the originally prepared calibration curves lose their accuracy if the polymer structures change, for instance an acrylic acid ester mer unit being hydrolyzed to an acrylic acid mer unit.
Polymers tagged with pendant fluorescent groups are capable of being monitored, even when present at low concentrations. Some polymers tagged with pendant fluorescent groups are known. A process for preparing a polymer from the copolymerization of a fluorescent compound wherein an acrylamide moiety and the aromatic fluorescing moiety are directly linked through an amide bond to the aromatic ring is disclosed in Japanese Patent No. 1,141,147. Other fluorescent acrylamide based polymers are disclosed in U.S. Pat. Nos. 5,043,406 and 4,999,456. Polymers tagged with pendant fluorescent groups have been prepared by the transamidation derivatization of the pre-existing polymers having carbonyl-type pendant groups in U.S. Pat. No. 5,128,419. Another post-polymerization modification of a polyacrylamide with a fluorescing moiety is disclosed in U.S. Pat. No. 4,813,973. The preparation of certain vinylic coumarin derivatives is disclosed in Collection Czechoslov. Chem Common, Vol. 45, 1980, pgs. 727-731.
What are needed are additional fluorescent tagged polymers which can be used in variety of applications.
The first aspect of the invention is a water-soluble polymer of Formula Useful comprising from about 0.001 to about 10.0 mole percent of a Repeating Mer Unit represented by the formula: 
wherein a is an integer of from 1 to 10, R1 is selected from the group consisting of hydrogen and methyl groups, R2 and R3 are methyl groups, and R9 is selected from the group consisting of NH and O; TAG is a fluorescing moiety selected from the group consisting of: 
wherein the TAG is connected to the remainder of the mer unit thru the bond attached to the methylene group (xe2x80x94CH2xe2x80x94) at the xe2x80x9ctopxe2x80x9d of each TAG;
where R8 is methyl;
O-xcex2-Gal is xcex2-D-galactopyranoside;
and X, Xxe2x88x92a and Xxe2x88x92b are selected from the group consisting of chloride, iodide, sulfate, acetate, benzoate, phosphate and bromide;
wherein the polymer of Formula Useful also comprises from about 90.0 to about 99.999 mole percent of one or more one or more randomly distributed (with one or more randomly distributed including block configurations) water-soluble vinylic mer units selected from one or more monomer groups consisting of acrylamide, methacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, acrylic acid, sodium acrylate, ammonium acrylate, methacrylic acid, sodium methacrylate, ammonium methacrylate, dimethylaminoethyl acrylate methyl chloride quaternary salt, dimethylaminoethyl acrylate benzyl chloride quaternary salt, dimethylaminoethyl acrylate methyl sulfate quaternary salt, dimethylaminoethyl methacrylate methyl sulfate quaternary salt, dimethylaminopropyl acrylamide methyl sulfate quaternary salt, dimethylaminopropyl methacrylamide methyl sulfate quaternary salt, diallyldimethylammonium chloride, N-vinylformamide, dimethylaminoethyl methacrylate acid salts, including, but not limited to, sulfuric acid salts and hydrochloric acid salts, dimethylaminoethyl methacrylate methyl chloride quaternary salt, dimethylaminoethyl methacrylate benzyl chloride quaternary salt, methacrylamidopropyltrimethylammonium chloride, acrylamidopropyltrimethyl ammonium chloride, N,N-methylenebisacrylamide, triallylamine, acid salts of triallylamine, ethylene glycol dimethacrylate, N-vinyl pyrrolidone, 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS), the sodium salt of AMPS, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, sodium vinyl sulfonate, styrene sulfonate, maleic acid, sodium salt of maleic acid, ammonium salt of maleic acid, N-isopropylacrylamide, diethylene glycol dimethacrylate, triethylene glycol, dimethylacrylate and polyethylene glycol dimethacrylate.
TAG I is TAG Ia when R8 is H and X is Cl.
TAG I is TAG Ib when R8 is CH3 and X is Cl.
The second aspect of this invention are fluorescent monomers selected from the group consisting of: 
Where a, R1, R2, R3, R8 and R9 are as defined previously,
where R6 is either hydrogen or methyl; and
where R7 is either hydrogen or methyl.
The third aspect of this invention is the use of a polymer of Formula Useful as a water-soluble treatment agent; wherein said polymer of Formula Useful comprises from about 0.001 to about 10.0 mole percent of a Repeating Mer Unit represented by the formula: 
wherein a is an integer of from 1 to 10, R1 is selected from the group consisting of hydrogen and methyl groups, R2 and R3 are methyl groups, and R9 is selected from the group consisting of NH and O; TAG is a fluorescing moiety selected from the group consisting of: 
wherein the TAG is connected to the remainder of the mer unit thru the bond attached to the methylene group (xe2x80x94CH2xe2x80x94) at the xe2x80x9ctopxe2x80x9d of each TAG;
where R8 is methyl,
O-xcex2-Gal is xcex2-D-galactopyranoside;
and X, Xxe2x88x92a and Xxe2x88x92b are selected from the group consisting of chloride, iodide, sulfate, acetate, benzoate, phosphate and bromide;
wherein the polymer of Formula Useful also comprises from about 90.0 to about 99.999 mole percent of one or more randomly distributed (with one or more randomly distributed including block configurations) water-soluble vinylic mer units selected from one or more monomer groups consisting of acrylamide, methacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, acrylic acid, sodium acrylate, ammonium acrylate, methacrylic acid, sodium methacrylate, ammonium methacrylate, dimethylaminoethyl acrylate methyl chloride quaternary salt, dimethylaminoethyl acrylate benzyl chloride quaternary salt, dimethylaminoethyl acrylate methyl sulfate quaternary salt, dimethylaminoethyl methacrylate methyl sulfate quaternary salt, dimethylaminopropyl acrylamide methyl sulfate quaternary salt, dimethylaminopropyl methacrylamide methyl sulfate quaternary salt, diallyldimethylammonium chloride, N-vinylformamide, dimethylaminoethyl methacrylate acid salts, including, but not limited to, sulfuric acid salts and hydrochloric acid salts, dimethylaminoethyl methacrylate methyl chloride quaternary salt, dimethylaminoethyl methacrylate benzyl chloride quaternary salt, methacrylamidopropyltrimethylammonium chloride, acrylamidopropyltrimethylammonium chloride, N,N-methylenebisacrylamide, triallylamine, acid salts of triallylamine, ethylene glycol dimethacrylate, N-vinyl pyrrolidone, 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS), the sodium salt of AMPS, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxypropylmethacrylate, sodium vinyl sulfonate, styrene sulfonate, maleic acid, sodium salt of maleic acid, ammonium salt of maleic acid, N-isopropylacrylamide, diethylene glycol dimethacrylate, triethylene glycol, dimethylacrylate and polyethylene glycol dimethacrylate.
The fourth aspect of this invention is a method for maintaining the desired amount of water-soluble polymeric treating agents added to water comprising the steps of:
a) adding a water-soluble polymeric treating agent of Formula Useful to water such that a desired concentration of water-soluble polymeric treating agent of Formula Useful is present in said water, wherein said water-soluble polymeric treating agent of Formula Useful comprises from about 0.001 to about 10.0 mole percent of a Repeating Mer Unit represented by the formula: 
xe2x80x83wherein a is an integer of from 1 to 10, R1 is selected from the group consisting of hydrogen and methyl groups, R2 and R3 are methyl groups, and R9 is selected from the group consisting of NH and O; TAG is a fluorescing moiety selected from the group consisting of: 
xe2x80x83wherein the TAG is connected to the remainder of the mer unit thru the bond attached to the methylene group (xe2x80x94CH2xe2x80x94) at the xe2x80x9ctopxe2x80x9d of each TAG;
where R8 is methyl;
O-xcex2-Gal is xcex2-D-galactopyranoside;
and X, Xxe2x88x92a and Xxe2x88x92b are selected from the group consisting of chloride, iodide, sulfate, acetate, benzoate, phosphate and bromide;
wherein the polymer of Formula Useful also comprises from about 90.0 to about 99.999 mole percent of one or more randomly distributed (with one or more randomly distributed including block configurations) water-soluble vinylic mer units selected from one or more monomer groups consisting of acrylamide, methacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, acrylic acid, sodium acrylate, ammonium acrylate, methacrylic acid, sodium methacrylate, ammonium methacrylate, dimethylaminoethyl acrylate methyl chloride quaternary salt, dimethylaminoethyl acrylate benzyl chloride quaternary salt, dimethylaminoethyl acrylate methyl sulfate quaternary salt, dimethylaminoethyl methacrylate methyl sulfate quaternary salt, dimethylaminopropyl acrylamide methyl sulfate quaternary salt, dimethylaminopropyl methacrylamide methyl sulfate quaternary salt, diallyldimethylammonium chloride, N-vinylformamide, dimethylaminoethyl methacrylate acid salts, including, but not limited to, sulfuric acid salts and hydrochloric acid salts, dimethylaminoethyl methacrylate methyl chloride quaternary salt, dimethylaminoethyl methacrylate benzyl chloride quaternary salt, methacrylamidopropyltrimethylammonium chloride, acrylamidopropyltrimethylammonium chloride, N,N-methylenebisacrylamide, triallylamine, acid salts of triallylamine, ethylene glycol dimethacrylate, N-vinyl pyrrolidone, 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS), the sodium salt of AMPS, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, sodium vinyl sulfonate, styrene sulfonate, maleic acid, sodium salt of maleic acid, ammonium salt of maleic acid, N-isopropylacrylamide, diethylene glycol dimethacrylate, triethylene glycol, dimethylacrylate and polyethylene glycol dimethacrylate;
b) analyzing the emissivity of said water as a measure of the concentration of said water-soluble polymeric treating agent of Formula Useful;
c) determining from the analysis of step b) that a change in concentration of said water-soluble polymeric treating agent of Formula Useful from the original concentration has occurred; and
d) adjusting the concentration of said polymeric treating agent accordingly.
The fifth aspect of this invention is a method for determining the efficiency of water-soluble polymeric treating agents added to water comprising the steps of:
a) combining a predetermined amount of said water-soluble polymeric treating agent with a predetermined effective indicating amount of a water-soluble indicator polymer of Formula Useful, wherein said water-soluble indicator polymer of Formula Useful comprises from about 0.001 to about 10.0 mole percent of a Repeating Mer Unit represented by the formula: 
xe2x80x83wherein a is an integer of from 1 to 10, R1 is selected from the group consisting of hydrogen and methyl groups, R2 and R3 are methyl groups, and R9 is selected from the group consisting of NH and O; TAG is a fluorescing moiety selected from the group consisting of: 
xe2x80x83wherein the TAG is connected to the remainder of the mer unit thru the bond attached to the methylene group (xe2x80x94CH2xe2x80x94) at the xe2x80x9ctopxe2x80x9d of each TAG;
where R8 is methyl;
O-xcex2-Gal is xcex2-D-galactopyranoside;
and X, Xxe2x88x92a and Xxe2x88x92b are selected from the group consisting of chloride, iodide, sulfate, acetate, benzoate, phosphate and bromide;
wherein the polymer of Formula Useful also comprises from about 90.0 to about 99.999 mole percent of one or more randomly distributed (with one or more randomly distributed including block configurations) water-soluble vinylic mer units selected from one or more monomer groups consisting of acrylamide, methacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, acrylic acid, sodium acrylate, ammonium acrylate, methacrylic acid, sodium methacrylate, ammonium methacrylate, dimethylaminoethyl acrylate methyl chloride quaternary salt, dimethylaminoethyl acrylate benzyl chloride quaternary salt, dimethylaminoethyl acrylate methyl sulfate quaternary salt, dimethylaminoethyl methacrylate methyl sulfate quaternary salt, dimethylaminopropyl acrylamide methyl sulfate quaternary salt, dimethylaminopropyl methacrylamide methyl sulfate quaternary salt, diallyldimethylammonium chloride, N-vinylformamide, dimethylaminoethyl methacrylate acid salts, including, but not limited to, sulfuric acid salts and hydrochloric acid salts, dimethylaminoethyl methacrylate methyl chloride quaternary salt, dimethylaminoethyl methacrylate benzyl chloride quaternary salt, methacrylamidopropyltrimethylammonium chloride, acrylamidopropyltrimethylammonium chloride, N,N-methylenebisacrylamide, triallylamine, acid salts of triallylamine, ethylene glycol dimethacrylate, N-vinyl pyrrolidone, 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS), the sodium salt of AMPS, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, sodium vinyl sulfonate, styrene sulfonate, maleic acid, sodium salt of maleic acid, ammonium salt of maleic acid, N-isopropylacrylamide, diethylene glycol dimethacrylate, triethylene glycol, dimethylacrylate and polyethylene glycol dimethacrylate;
b) adding said water-soluble indicator polymer of Formula Useful and said water-soluble polymeric treating agent to said water;
c) analyzing the emissivity of said water as a measure of the concentration of said indicator polymer;
d) determining from the analysis of step c) that a change in concentration of said indicator polymer from said predetermined amount has occurred;
e) determining that a proportional change in said amount of said polymeric treating agent has occurred; and
f) adjusting the concentration of said polymeric treating agent accordingly such that the desired concentration of said polymeric treating agent is present in said water.
Throughout this patent application, the following definitions will be used:
AcAm for acrylamide.
AIBN for 2,2xe2x80x2-azobis(isobutyronitrile)
AIR PRODUCTS for Air Products and Chemicals, Inc., 7201 Hamilton Boulevard, Allentown, Pa. 18195-1501, telephone number (610) 481-4911.
AIVN for 2,2xe2x80x2-azobis(2,4-dimethylvaleronitrile).
ALDRICH for Aldrich Chemical Company, P.O. Box 2060, Milwaukee, Wis., 53201, telephone numbers (414) 273-3850 or (800) 558-9160.
cP for centipoise.
Chain Transfer Agent is used for any molecule, used in free-radical polymerization, which will react with a polymer radical forming a dead polymer and a new radical. Representative Chain Transfer Agents are listed by K. C. Berger and G. Brandrup, xe2x80x9cTransfer Constants to Monomer, Polymer, Catalyst, Solvent, and Additive in Free Radical Polymerization,xe2x80x9d Section II, pp. 81-151, in xe2x80x9cPolymer Handbook,xe2x80x9d edited by J. Brandrup and E. H. Immergut, 3d edition, 1989, John Wiley and Sons, New York.
Cross-Linking Agent for an ethylenically unsaturated monomer containing at least two sites of ethylenic unsaturation which is added to branch or increase the molecular weight of the water-soluble fluorescent polymer of this invention. Representative Cross-Linking Agents include N,N-methylenebisacrylamide, N,N-methylenebismethacrylamide, polyethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, N-vinyl acrylamide, divinyl benzene, triallyl ammonium salts, N-methyl allylacrylamide, glycidyl acrylate, acrolein, methylolacrylamide, glyoxal, epichlorohydrin, and the like. The cross linker is added at from about 0.0001 to about 10, preferably from about 0.0001 to about 0.2 weight percent based on the weight of the polymer.
Branching Agent for a Cross-Linking Agent that is administered at a low level (less than 0.05 weight percent based on the weight of the polymer). It is understood that Branching Agents are added to form xe2x80x9cbranchesxe2x80x9d not cross-links.
DADMAC for diallyldimethylammonium chloride.
DMAEA for dimethylaminoethyl acrylate.
DMAEM for dimethylaminoethyl methacrylate.
DMAEA.BCQ for dimethylaminoethyl acrylate, benzyl chloride quaternary salt.
DMAEA.MCQ for dimethylaminoethyl acrylate, methyl chloride quaternary salt.
DMAPMA for dimethylaminopropylmethacrylamide.
DMAPAA for dimethylaminopropylacrylamide
DMF for dimethylformamide.
DOW for The Dow Chemical Company, 2020 Dow Center, Midland Mich. 48686-0440, telephone numbers (517) 496-4000.
DUPONT for E. I. duPont de Nemours and Co. Inc., 1007 Market Street, Wilmington, Del. 19898, telephone numbers U.S. (800) 441-7515; worldwide (302) 774-1000.
EDTA.4Na+ for ethylenediaminetetraacetic acid, tetrasodium salt.
EXXON for Exxon Chemical Co., 13501 Caty Freeway, Houston, Tex. 77079-1398, telephone number (281) 870-6712.
Halomethylfluorochrome for a fluorescent moiety which contains a xe2x80x94CH2-halo component where halo is chloro, bromo or iodo. A halomethylfluorochrome can be used to form fluorescent quaternary (water soluble) monomers by reacting the halomethylfluorochrome with a tertiary amine containing monomer (DMAEA, DMAPMA, etc.).
HLB for hydrophilic-lipophilic balance number.
1H-NMR for Proton Nuclear Magnetic Resonance Spectroscopy.
ICI for ICI Specialty Chemicals, Concord Plaza, 3411 Silverside Road, Wilmington, Del., telephone number (302) 887-3000.
KOHJIN for Kohjin Co., Ltd., 1-1, 1-Chome, Shimbashi, Minato-Ku, Tokyo, Japan, telephone number (03) 3504-3129.
MEHQ for the mono methyl ether of hydroquinone (4-methoxyphenol). mmol for millimole.
MOLECULAR PROBES for Molecular Probes, Inc., 4849 Pitchford Avenue, Eugene Oreg. 97402-9165, telephone number (541) 465-8300.
NaCl for sodium chloride.
ROHM and HAAS is Rohm and Haas, 100 Independence Mall West, Philadelphia, Pa. 19106-2399, telephone number (215) 592-3000.
TLC for Thin-Layer Chromatography.
TRC for Toronto Research Chemicals, Inc., 2 Brisbane Rd., North York, ON M3J 2J8, telephone number 1-800-727-9240.
V-50 for 2,2xe2x80x2-azobis-(2-amidinopropane) dihydrochloride.
V-501 for 4,4xe2x80x2-azobis-(4-cyanopentanoic acid).
Versenex(copyright)80 for the pentasodium salt of diethylenetriaminepentaacetic acid.
WAKO for Wako Chemicals USA, Inc., 1600 Bellwood Road, Richmond, Va. 23237, (804) 714-1920 or (800) 992-9256.
Indicator polymer, tagged polymer and fluorescent polymer are used interchangeably, and are meant to describe the polymers of the instant invention which are capable of fluorescing as a result of incorporation of a fluorescent moiety during polymerization.
RSV stands for Reduced Specific Viscosity. RSV is an indication of polymer chain length and average molecular weight. The RSV is measured at a given polymer concentration and temperature and calculated as follows:       RSV    =                  [                              (                          η              /                              η                o                                      )                    -          1                ]            c            η    =          viscosity      ⁢              xe2x80x83            ⁢      of      ⁢              xe2x80x83            ⁢      polymer      ⁢              xe2x80x83            ⁢      solution                  η      o        =          viscosity      ⁢              xe2x80x83            ⁢      of      ⁢              xe2x80x83            ⁢      solvent      ⁢              xe2x80x83            ⁢      at      ⁢              xe2x80x83            ⁢      the      ⁢              xe2x80x83            ⁢      same      ⁢              xe2x80x83            ⁢      temperature            c    =          concentration      ⁢              xe2x80x83            ⁢      of      ⁢              xe2x80x83            ⁢      polymer      ⁢              xe2x80x83            ⁢      in      ⁢              xe2x80x83            ⁢              solution        .            
In this patent application, the units of concentration xe2x80x9ccxe2x80x9d are (grams/100 ml or g/deciliter). Therefore, the units of RSV are dl/g. In this patent application, for measuring RSV, the solvent used was 1.0 molar sodium nitrate solution. The polymer concentration in this solvent was 0.045 g/dl. The RSV was measured at 30xc2x0 C. unless otherwise indicated. The viscosities xcex7 and xcex7o were measured using a Cannon Ubbelohde semimicro dilution viscometer, size 75. The viscometer is mounted in a perfectly vertical position in a constant temperature bath adjusted to 30xc2x10.02xc2x0 C. The error inherent in the calculation of RSV is about 2 dl/grams. Within a series of polymer homologs, which are substantially linear, and well-solvated, polymers with similar RSV""s have similar molecular weights according to Paul J. Flory, in xe2x80x9cPrinciples of Polymer Chemistryxe2x80x9d, Cornell University Press, Ithaca, N.Y., (copyright) 1953, Chapter VII, xe2x80x9cDetermination of Molecular Weightsxe2x80x9d, pp. 266-316.
IV stands for intrinsic viscosity, which is RSV extrapolated to the limit of infinite dilution, infinite dilution being when the concentration of polymer is equal to zero.
The present invention is a water-soluble polymer of Formula Useful comprising from about 0.001 to about 10 mole percent of a Repeating Mer Unit represented by the formula: 
wherein a is an integer of from 1 to 10, R1 is selected from the group consisting of hydrogen and methyl groups, R2 and R3 are methyl groups, R9 is selected from the group consisting of NH and O; and TAG is a fluorescing moiety selected from the group consisting of: TAG I, TAG II, TAG III, TAG IV, TAG V, TAG VI, TAG VII, TAG VIIIa, TAG VIIIb, TAG IX, TAG X, TAG XI, TAG XIIa, TAG XIIb, TAG XIIc and TAG XIII; wherein the TAG is connected to the remainder of the mer unit thru the bond attached to the methylene group (xe2x80x94CH2xe2x80x94) at the xe2x80x9ctopxe2x80x9d of each TAG;
where R8 is methyl;
O-xcex2-Gal is xcex2-D-galactopyranoside;
and X, Xxe2x88x92a and Xxe2x88x92b are selected from the group consisting of chloride, iodide, sulfate, acetate, benzoate, phosphate and bromide ions;
wherein the polymer of Formula Useful also comprises from about 90.0 to about 99.999 mole percent of one or more randomly distributed (with one or more randomly distributed including block configurations) water-soluble vinylic mer units selected from one or more of the monomer groups consisting of acrylamide, methacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, acrylic acid, sodium acrylate, ammonium acrylate, methacrylic acid, sodium methacrylate, ammonium methacrylate, dimethylaminoethyl acrylate methyl chloride quaternary salt, dimethylaminoethyl acrylate benzyl chloride quaternary salt, dimethylaminoethyl acrylate methyl sulfate quaternary salt, dimethylaminoethyl methacrylate methyl sulfate quaternary salt, dimethylaminopropyl acrylamide methyl sulfate quaternary salt, dimethylaminopropyl methacrylamide methyl sulfate quaternary salt, diallyldimethylammonium chloride, N-vinylformamide, dimethylaminoethyl methacrylate acid salts, including, but not limited to, sulfuric acid salts and hydrochloric acid salts, dimethylaminoethyl methacrylate methyl chloride quaternary salt, dimethylaminoethyl methacrylate benzyl chloride quaternary salt, methacrylamidopropyltrimethylammonium chloride, acrylamidopropyltrimethylammonium chloride, N,N-methylenebisacrylamide, triallylamine, acid salts of triallylamine, ethylene glycol dimethacrylate, N-vinyl pyrrolidone, 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS), the sodium salt of AMPS, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxypropylmethacrylate, sodium vinyl sulfonate, styrene sulfonate, maleic acid, sodium salt of maleic acid, ammonium salt of maleic acid, N-isopropylacrylamide, diethylene glycol dimethacrylate, triethylene glycol, dimethylacrylate and polyethylene glycol dimethacrylate.
Synthesis of Polymers
The first step in the synthesis of the polymers is to obtain the required monomer units.
Monomers I through III, VII, XIIa, XIIb, XIIc and XIII can be obtained by following this general procedure: A sample of a halomethyl fluorochrome is charged into a reaction flask along with acetone and a few crystals of MEHQ. The reaction mixture is heated to 56xc2x0 C. To the resulting solution is added 3.3 molar equivalents of DMAPMA, DMAPAA, DMAEA, or DMAEM. The resulting mixture is refluxed until the vinylic quaternary salt (fluroescent vinylic monomer) is formed, typically in less than 2 hours. The progress of the reaction may be monitored by TLC. The reaction mixture is cooled, and the resulting precipitate is removed by filtration, washed with cold acetone and dried, yielding the fluorescent vinylic monomer as a solid.
Monomer IV can be obtained by following this general procedure: A mixture of 2-(chloromethyl)quinoline.HCl and a 1% sodium carbonate solution is added to a separatory funnel, and extracted with methylene chloride. The methylene chloride extracts are passed through a cone of anhydrous sodium sulfate, and collected in a flask. 2-(Chloromethyl)quinoline is obtained in the flask after evaporation of the methylene chloride. To the flask containing 2-(chloromethyl)quinoline, is added MEHQ and acetone. The mixture is heated to about 56xc2x0 C. DMAPMA is added to the solution. The resulting mixture is heated for about 110 min at 56xc2x0 C., then cooled to about 25xc2x0 C. for 2 hrs. The resulting white solid, the quaternary ammonium salt of DMAPMA and 2-(chloromethyl)quinoline, is isolated by filtration.
Monomer V and VI and VIIIa and VIIIb and IX and X and XI can be obtained by following this general procedure: A sample of the halomethyl flurorochrome, a few crystals of MEHQ and DMF is charged into a reaction flask. To the resulting solution is added about 3.3 equivalents of DMAPMA, DMAPAA, DMAEA or DMAEM. The resulting solution is heated to about 60xc2x0 C. and maintained at that temperature until the quaternary monomer is formed. The progress of the reaction can be followed by using TLC. The resulting mixture is cooled, and used as a solution of the fluorescent vinylic monomer in DMF.
Suitable vinylic mer units are selected from one or more of the monomer groups consisting of acrylamide, methacrylamide, acrylic acid, sodium acrylate, ammonium acrylate, methacrylic acid, sodium methacrylate, ammonium methacrylate, dimethylaminoethyl acrylate methyl chloride quaternary salt, dimethylaminoethyl acrylate benzyl chloride quaternary salt, dimethylaminoethyl acrylate methyl sulfate quaternary salt, dimethylaminoethyl methacrylate methyl sulfate quaternary salt, dimethylaminopropyl acrylamide methyl sulfate quaternary salt, dimethylaminopropyl methacrylamide methyl sulfate quaternary salt, diallyldimethyl ammonium chloride, N-vinyl formamide, dimethylamino ethyl methacrylate acid salts, including, but not limited to, sulfuric acid salts and hydrochloric acid salts, dimethylaminoethyl methacrylate methyl chloride quaternary salt, dimethylaminoethyl methacrylate benzyl chloride quaternary salt, methacrylamidopropyl trimethyl ammonium chloride, acrylamidopropyl trimethyl ammonium chloride, methylene bis acrylamide, triallylamine, acid salts of triallylamine, ethyleneglycol dimethacrylate, N-vinyl pyrrolidone, 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS), the sodium salt of AMPS, hydroxyethylmethacrylate, hydroxyethylacrylate, hydroxypropylacrylate, hydroxypropylmethacrylate, sodium vinyl sulfonate, styrene sulfonate, maleic acid, sodium salt of maleic acid, ammonium salt of maleic acid, N-isopropylacrylamide, diethylene glycol dimethacrylate, triethylene glycol, dimethylacrylate and polyethylene glycol dimethacrylate.
These monomers can be synthesized using techniques known to a person of ordinary skill in the art of polymer synthesis or they can be purchased from ALDRICH or other sources. For example, hydroxyethylmethacrylate, hydroxyethylacrylate, hydroxypropylacrylate and hydroxypropyl methacrylate are available under the ROCRYL(copyright) trademark from ROHM and HAAS. Sodium vinyl sulfonate can be obtained from AIR PRODUCTS. N-isopropyl acrylamide is available from KOHJIN.
Polymers of Formula Useful contain at least two monomers: one monomer is selected from the group consisting of MONOMER I, MONOMER II, MONOMER III, MONOMER IV, MONOMER V, MONOMER VI, MONOMER VII, MONOMER VIIIa, MONOMER VIIIb, MONOMER IX, MONOMER X, MONOMER XI, MONOMER XIIa, MONOMER XIIb, MONOMER XIIc, and MONOMER XIII. The other monomer is selected from the group of suitable vinylic mer units previously listed. The mole percents of each monomer in polymers of Formula Useful have been previously given. In polymers of Formula Useful, it is possible to have one or more mer units selected from the group consisting of suitable vinylic mer units previously given. Preferred suitable vinylic mer units or combinations of suiltable vinylic mer units include: DADMAC, acrylic acid, a combination of acrylamide and DMAEA.MCQ, and a combination of acrylamide and DADMAC.
After all of the requisite monomers have been obtained, Polymers of Formula Useful can be synthesized by following the procedure for making water-in-oil emulsion polymers or the procedure for making dispersion polymers or the procedure for making dry polymers or the procedure for making solution polymers.
The preparation of high molecular weight water-in-oil emulsion polymers has been described in the following references: U.S. Pat. No. 2,982,749 assigned to The Dow Chemical Company; U.S. Pat. No. 3,284,393 assigned to The Dow Chemical Company; U.S. Pat. No. 3,734,873 assigned to Nalco Chemical Company; xe2x80x9cMechanism, Kinetics and Modeling of the Inverse-Microsuspension Homopolymerization of Acrylamide,xe2x80x9d by Hunkeler, D., Hamielec, A. and Baade, W., Polymer (1989), 30(1), 127-42; and xe2x80x9cMechanism, Kinetics and Modeling of Inverse-Microsuspension Polymerization: 2. Copolymerization of Acrylamide with Quaternary Ammonium Cationic Monomers,xe2x80x9d by D. Hunkeler and A. E. Hamielec, A. E.; Polymer (1991), 32(14), 2626-40.
A general procedure for the manufacture of water-in-oil emulsion polymers is provided to illustrate the preparation of these polymers using fluorescent monomers. The types and quantities of specific components in the formula (monomers, initiators, Chain Transfer Agents, for example) will vary depending upon the type of polymer (cationic, anionic, nonionic) that is being synthesized.
An aqueous phase is prepared by mixing together in water one or more water soluble monomers, and different polymerization additives such as inorganic salts, chelants, pH buffers, Chain Transfer Agents and Branching or Cross-Linking Agents. In order to synthesize the fluorescent water-soluble polymers of the instant claimed invention, a monomer selected from the group of Monomer I through Monomer XIII is included in the aqueous phase at the desired level.
An organic phase is prepared by mixing together an inert hydrocarbon liquid with one or more oil soluble surfactants. The surfactant mixture should have a low HLB, to ensure the formation of an oil continuous emulsion. Appropriate surfactants for water-in-oil emulsion polymerizations, which are commercially available, are compiled in the North American Edition of McCutcheon""s Emulsifiers and Detergents. The oil phase may need to be heated to ensure the formation of a homogeneous oil solution in a reasonable amount of time.
The oil phase is charged into a reactor equipped with a mixer, a thermocouple, a nirogen purge tube, and a condenser. Adding the aqueous phase to the reactor containing the oil phase with vigorous stirring forms an emulsion. The resulting emulsion is heated to the desired temperature, purged with nitrogen, and a free-radical initiator is added. The reaction mixture is stirred for several hours under a nitrogen atmosphere at the desired temperature. Upon completion of the reaction, the water-in-oil emulsion polymer is cooled to room temperature, where any desired post-polymerization additives, such as antioxidants, or a high HLB surfactant (as described in U.S. Pat. No. 3,734,873) may be added.
The resulting emulsion polymer is a free-flowing liquid. An aqueous solution of the water-in-oil emulsion polymer can be generated by adding a desired amount of the emulsion polymer to water with vigorous mixing in the presence of a high-HLB surfactant (as described in U.S. Pat. No. 3,734,873).
The preparation of dispersion polymers has been described in the following references: U.S. Pat. No. 4,929,655, assigned to Hymo Corporation; U.S. Pat. No. 5,006,590, assigned to Hymo Corporation; U.S. Pat. No. 5,597,859, assigned to Nalco Chemical Company; European Patent 657,478; U.S. Pat. No. 5,597,858, assigned to Nalco Chemical Company and European Patent 630,909.
A general procedure for the manufacture of dispersion polymers is provided below in order to illustrate the preparation of dispersion polymers comprising the fluorescent monomers described herein. The types and quantities of specific components in the formula (salts and stabilizer polymers, for example) will vary depending upon the type of polymer (cationic, anionic, nonionic) that is being synthesized.
An aqueous solution containing one or more inorganic salts, one or more water-soluble monomers, any polymerization additives such as chelants, pH buffers, Chain Transfer Agents, Branching or Cross-Linking Agents and a water-soluble stabilizer polymer is charged to a reactor equipped with a mixer, a thermocouple, a nitrogen purging tube, and a water condenser. The monomer solution is mixed vigorously, heated to the desired temperature, and then a water-soluble initiator is added. The solution is purged with nitrogen whilst maintaining temperature and mixing for several hours. After this time, the products are cooled to room temperature, and any post-polymerization additives are charged to the reactor. Water continuous dispersions of water-soluble polymers are free flowing liquids with product viscosities generally 100-10,000 cP, measured at low shear. Thus, in order to prepare fluorescent water-soluble polymers as dispersions, a monomer selected from the group of Monomer I through Monomer XIII is included in the reaction mixture at the desired level.
A general procedure for the manufacture of dry powder polymers is provided below in order to illustrate the preparation of dry polymers comprising the fluorescent monomers described herein. The types and quantities of specific components in the formula (monomers, initiators, Chain Transfer Agents, for example) will vary depending upon the type of polymer (cationic, anionic, nonionic) that is being synthesized.
An aqueous solution of water-soluble monomers, generally 20-60 percent concentration by weight, along with any polymerization or process additives such as Chain Transfer Agents, Branching or Cross-Linking Agents, chelants, pH buffers, or surfactants, is warmed to an appropriate temperature and placed in an insulated reaction vessel equipped with a nitrogen purging tube. A polymerization initiator is added, the solution is purged with nitrogen, and the temperature of the reaction is allowed to rise uncontrolled. When the polymerized mass is cooled, the resultant gel is removed from the reactor, shredded, dried, and ground to the desired particle size. Thus, in order to prepare fluorescent water-soluble polymers as dry powders, a monomer selected from the group of Monomer I through Monomer XIII is included in the reaction mixture at the desired level.
A general procedure for the manufacture of solution polymers is provided to illustrate the preparation of these polymers using fluorescent monomers. The types and quantities of specific components in the formula (monomers, initiators, Chain Transfer Agents, for example) will vary depending upon the type of polymer (cationic, anionic, nonionic) that is being synthesized:
An aqueous solution containing one or more water soluble monomers and any polymerization additives such as chelants, pH buffers or Chain Transfer Agents is prepared. This mixture is charged to a reactor equipped with a mixer, a thermocouple, a nitrogen purging tube and a water condenser. The solution is mixed vigorously, heated to the desired temperature, and then one or more water soluble free radical polymerization initiators are added. The solution is purged with nitrogen whilst maintaining temperature and mixing for several hours. Typically, the viscosity of the solution increases during this period. After the polymerization is complete, the reactor contents are cooled to room temperature and then transferred to storage. Solution polymer viscosities vary widely, and are dependent upon the concentration and molecular weight of the active polymer component. Thus, in order to prepare fluorescent water soluble solution polymers, a monomer selected from the group of Monomer I through Monomer XIII is included in the reaction mixture at the desired level.
Once synthesized, the polymers of Formula Useful are useful as water soluble polymeric treatment agents.
One such utility for the polymers of Formula Useful is their use in the dewatering of sludge. The typical amount of polymer used in dewatering of sludge is from about 3 ppm to about 1000 ppm, preferably from about 10 ppm to about 400 ppm and most preferably from about 20 ppm to about 200 ppm.
Another utility for the polymers of Formula Useful is their use as retention and drainage aids. The polymer functions as a flocculant during the papermaking process with the flocculant added to enhance the retention and drainage properties of the pulp/paper. Retention and drainage are important properties of a papermaking process that papermakers are always seeking to optimize. Details concerning the art of making paper and the necessity for having acceptable retention and drainage properties of the pulp/paper during processing can be found in any standard reference text in the art of papermaking. Once such text, is xe2x80x9cPAPER BASICS: Forestry, Manufacture, Selection, Purchasing, Mathematics and Metrics, Recyclingxe2x80x9d, by David Saltman, (copyright) 1978 by Van Norstrand Reinhold Company, published by Krieger Publishing Company, Krieger Drive, Malabar, Fla. 32950.
The typical amount of polymer used for a retention and drainage aid in pulp and paper applications is from about 0.25 lbs active/ton of solids in furnish to about 6.0 lbs active/ton of solids. More preferably, the amount of polymer added is from about 0.5 lbs active/ton of solid in furnish to about 4 lbs active/ton of solids in furnish and most preferably, the amount of the polymer added is about 2 lbs actives/ton of solids in furnish. The dose of polymer recited herein is based on pounds of actual polymer, not pounds of liquid that contains polymer.
The polymers of Formula Useful can be used in a method for maintaining the desired amount of water-soluble polymeric treating agent of Formula Useful added to water comprising the steps of:
a) adding a water-soluble polymeric treating agent of Formula Useful to water such that a desired concentration of water-soluble polymeric treating agent of Formula Useful is present in said water;
b) analyzing the emissivity of said water as a measure of the concentration of said water-soluble polymeric treating agent of Formula Useful;
c) determining from the analysis of step b) that a change in concentration of said water-soluble polymeric treating agent of Formula Useful from the original concentration has occurred; and
d) adjusting the concentration of said polymeric treating agent accordingly.
The waters may be either natural or industrial waters. Natural waters are also referred to as xe2x80x9cuntreatedxe2x80x9d or xe2x80x9crawxe2x80x9d waters. The industrial waters may be municipal wastewaters, chemical processing wastewaters, boiler water, cooler water, water utilized in papermaking and mining applications and water used in any other industrial application which requires treatment.
The xe2x80x9cdesired concentration of water-soluble polymeric treating agent of Formula Usefulxe2x80x9d is known or readily determinable by experiments that are known to one of ordinary skill in the art. It is also known that the concentration of water-soluble polymeric treating agent of Formula Useful can be indirectly measured by measuring the emissivity of the water sample. The standard technique of relating emissivity to concentration is by the use of a calibration curve for each polymer that plots emissivity against the known concentration of polymer in the sample. A person of ordinary skill in the art also would know how to create these calibration curves.
As utilized herein, the term xe2x80x9canalyzing the emissivityxe2x80x9d refers to monitoring by a fluorescence technique. Such techniques, and required calculations to correlate fluorescence to concentration are described in U.S. Pat. Nos. 4,783,314; 4,992,380; 5,171,450; and 5,435,969; which are hereby incorporated by reference.
By the term xe2x80x9cadjusting the concentration of said polymeric treating agent accordinglyxe2x80x9d is meant that the amount of the water-soluble polymeric treating agent of Formula Useful being added to said water is adjusted based on some significant change in the fluorescence measurement. The actual fluorescence measurement may either increase or decrease depending on the application, as a function of polymer dosage, or the relative changes in the fluorescence measurement may either become larger or smaller as a function of polymer dosage. When such changes occur at or near the optimum polymer dosage as represented by some other parameter of interest (for example drainage, retention, sludge dewatering, etc.) then the trends in the fluorescence measurement can be used to determine and maintain the proper dosage of the polymeric treating agent for the particular parameter of interest. The method is particularly suited to applications where such instantaneous feedback could be provided by an in-line fluorescence monitoring device which would be used as part of a system to control a polymer feeding pump, for example, wherein the polymer dosage is increased or decreased depending on the response from the fluorescence measurement device.
For instance, it may be desirable to monitor water treatment polymers in water systems, particularly industrial water systems, or to monitor polymers that may be present in waste fluids before disposal, particularly industrial waste fluids, or to monitor the polymer used for down-hole oil well applications, particularly the route taken after introduction down-hole, or to monitor polymers that may be present in fluids used to wash a manufactured product, for instance a polymer-coated product, to determine the amount of polymer washed or leached therefrom. By fluids or liquids as used herein generally is meant aqueous, non-aqueous, and mixed aqueous/non-aqueous fluid systems. In addition, the polymers of Formula Useful can be used in a method for determining the efficiency of water-soluble polymeric treating agents added to water comprising the steps of:
a) combining a predetermined amount of said water-soluble polymeric treating agent with a predetermined effective indicating amount of a water-soluble indicator polymer of Formula Useful;
b) adding said water-soluble indicator polymer of Formula Useful and said water-soluble polymeric treating agent to said water;
c) analyzing the emissivity of said water as a measure of the concentration of said indicator polymer;
d) determining from the analysis of step c) that a change in concentration of said indicator polymer from said predetermined amount has occurred;
e) determining that a proportional change in said amount of said polymeric treating agent has occurred; and
f) adjusting the concentration of said polymeric treating agent accordingly such that the desired concentration of said polymeric treating agent is present in said water.
As used herein, the term water-soluble polymeric treating agent refers to polymers which are added to aqueous systems for the purpose of scale control, corrosion inhibition, dispersing polymers, flocculating polymers, coagulating polymers and thickening polymers among others. The term predetermined amount, in reference to the water-soluble polymeric treating agent, refers to an amount known to a person of normal skill in the art as being required by the system to effect a particular treatment. For example, if the water is a boiler water, the predetermined amount would be the effective scale-preventing amount of polymer required by that particular aqueous system to prevent scale. As used herein, the term predetermined effective indicating amount refers to a minimal amount that can be detected by a fluorescence technique (above the native fluorescence of the aqueous system being treated).
The water-soluble polymeric treating agent and the water-soluble polymeric indicator of Formula Useful may be blended prior to addition, or added individually in sequential fashion. Once they have been added to the system, the water can be analyzed fluorometrically to look for the indicator polymer. The amount of indicator polymer found is then used to calculate the amount of water-soluble polymeric treating agent present. The amount of water-soluble polymeric treating agent being added to the water is then adjusted either upwards or downwards in order to provide for the desired concentration of water-soluble polymeric treating agent in the water.